Liquid glycol benzoate compositions and polymer compositions containing same

ABSTRACT

The present invention relates to organic polymer compositions, containing liquid ester compositions as plastisizers, said compositions comprising mixtures of esters derived from (a) diethylene glycol and triethylene glycol and (b) benzoic or toluic acid, wherein the freezing point of the ester mixture is below the freezing points of the constituent esters when the relative concentrations of the constituent esters are within specified limits.

This Application is a division of Ser. No. 08/904,049, filed Jul. 31,1997, now U.S. Pat. No. 5,990,214.

FIELD OF THE INVENTION

This invention relates to liquid ester compositions. More particularly,this invention relates to mixtures of esters derived from certainaromatic monocarboxylic acids and specified combinations of oligomericand optionally monomeric ethylene glycols. These mixtures are liquids attemperatures below the freezing point of the individual constituentesters.

DESCRIPTION OF THE PRIOR ART

Esters derived from 1) benzoic or toluic acid and 2) an aliphatic glycolor oligomer thereof together with methods for preparing these esters aredescribed in the prior art.

Certain of these esters, particularly esters derived from glycolscontaining from 2 to about 9 carbon atoms, constitute a preferred classof plasticizers for polyvinyl chloride and other inherently rigidorganic polymers because of the ability of the esters to improve theprocessability of the rigid polymers without adversely affecting theirdesirable physical properties.

U.S. Pat. No. 4,656,214, which issued to Wickson on Apr. 7, 1987describes diesters of 1) linear glycols containing from 2 to 8 carbonatoms, 2) a first carboxylic acid of the formula R¹R²R³C(O)OH and 3) asecond carboxylic acid of the formula R⁵C(O)OH, wherein R¹ and R² areindividually selected from alkyl containing from 1 to 4 carbon atoms, R³is hydrogen or alkyl from 1 to 6 carbon atoms, R⁵ is selected from thegroup consisting of phenyl, mono- di- and trialkyl-substituted phenylcontaining from 9 to 12 carbon atoms and —(CH₂)_(n)Ph where Ph is phenyland the value of n is from 1 to 6, inclusive. The esters contain from 16to 19 carbon atoms and are useful as stain-resistant plasticizers forpolyvinyl chloride.

The use as plasticizers of esters derived from benzoic acid and apolyhydric alcohol is described in Japanese Laid Open Patent ApplicationNo. 54/18859, published on Feb. 13, 1979.

Published European Patent Application No. 244,107, issued on Nov. 4,1987 describes plasticizer compositions for elastomers comprising I) atrimellitate ester, II) a saturated linear dicarboxylate ester obtainedby reacting 1) a dicarboxylic acid with at least one monohydric alcoholor 2) an aliphatic monocarboxylic acid with at least one of diethyleneglycol, triethylene glycol and tetraethylene glycol, and III) a dialkylester of a thiodicarboxylic acid.

U.S. Pat. No. 4,444,933 to J. Anderson and P. Columbus describescyanoacrylate adhesives containing a plasticizer that is selected fromdipropylene glycol dibenzoate, diethylene glycol dibenzoate, a mixtureof the foregoing two compounds, butylbenzyl phthalate, dibutyl phthalateor a benzoate ester of di- or polyhydroxy branched aliphatic compounds.

Research Disclosure No. 17943, published on Mar. 10, 1979 describesplasticized road marking compositions containing from 10 to 50 weightpercent of a plasticizer described as a benzoic acid ester exemplifiedby glyceryl tribenzoate, neopenyl dibenzoate, triethyleneglycoldibenzoate and trimethylolethane tribenzoate or a polyester.

Esters derived from benzoic acid and either di- or triethylene glycolare particularly desirable because of the wider availability and lowercost of these glycols relative to the corresponding propylene glycols.One of the disadvantages of using benzoic or toluic acid esters ofethylene glycol, di- and triethylene glycol as plasticizers is thatthese esters are solids at 25°. Polymer compositions containing theseesters as additives typically require heating to at least the meltingpoint of the additive to uniformly blend the additive into thecomposition.

SUMMARY OF THE INVENTION

The present invention is based on the discovery that within a relativelylimited range of proportions blends containing the di- and triethyleneglycol esters of benzoic and toluic (methylbenzoic) acids are liquidsbelow the freezing point of the individual constituent esters.

When the present blends are used as plasticizers they can optionallyinclude at least one additional ester that is a liquid at 25° C. and isconventionally used as a plasticizer for organic polymers. Theadditional liquid ester(s) increases the relative concentration oftriethylene glycol ester relative to diethylene glycol ester that can bepresent in a composition that is liquid below the freezing points ofboth glycol esters.

DETAILED DESCRIPTION OF THE INVENTION

This invention provides liquid ester compositions comprising:

1) a first diester of the formula ArC(O) (OCH₂CH₂)₂O(O) CAr and

2) a second diester of the formula ArC(O) (OCH₂CH₂)₃O(O) CAr;

wherein Ar represents a phenyl or methylphenyl radical, and the freezingpoint of said compositions are below the freezing points said first andsecond diesters.

The weight ratio of said first diester to said second diester ispreferably from 1.22:1 to 9:1.

In preferred embodiments the first and second diesters preferablyconstitute at least 50 weight percent of the present liquid estercomposition. The remaining ingredients of these preferred embodimentsare esters exhibiting freezing points below 250° C. These additionalesters are derived from mono- or polyhydric alcohols and aromatic oraliphatic mono- and/or dicarboxylic acids. The presence of theseadditional liquid esters increases the concentration of the triethyleneglycol diester relative to the diethylene glycol diester that can bepresent in compositions that are liquid below the freezing point ofthese glycol diesters.

Examples of the additional liquid esters that can be present in theester compositions or the present invention include but are not limitedto 1) diesters derived from benzoic acid and diols containing from 3 to10 carbon atoms, 2) esters derived from benzoic acid and monohydricalcohols containing from 8 to 12 carbon atoms, 3) aliphatic esters ofthe formula R¹O(O)C(CH₂)_(m)C(O)OR¹, and 4) esters derived from phthalicacid and alcohols containing from 4 to 12 carbon atoms. In the precedingformula R¹ is an alkyl individually selected from the group consistingof alkyl and aryl radicals containing from 4 to 12 carbon atoms, and mrepresents an integer from 2 to 8. The combined weight of theseadditional plasticizers can constitute up to 50, and preferably from 10to 35 weight percent of the present liquid ester composition. It will beunderstood that suitable diols can contain hetero atoms such as oxygenin the hydrocarbon chain.

Specific examples of additional liquid esters that can be present in theester compositions of the present invention include but are not limitedto propylene glycol and dipropylene glycol dibenzoates, neopentyl glycoldibenzoate, dialkyl adipates, glutarates, azelates and sebacates,isodecyl benzoate and butyl benzyl phthalate.

The additional liquid esters described in the preceding paragraphs canconstitute up to 50 weight percent of the present liquid estercompositions. The presence of these optional liquid esters reduce toabout 0.5:1 the weight ratio of the present diethylene glycol benzoateor toluate to triethylene glycol benzoate or toluate required to yield aliquid ester composition at 28° C.

The present invention also provides compositions comprising 1) anorganic polymer such as polyvinyl chloride and 2) up to about 60 weightpercent of the present liquid ester compositions as plasticizers. Theester compositions can also be included as plasticizing additives inliquid compositions such as oils and lubricants.

The novelty of the present ester compositions resides in the lowerfreezing point of the compositions relative to the freezing temperaturesof the two required diesters that constitute at least 50 percent byweight of these compositions. For example, diethylene glycol dibenzoatefreezes from 28-29° C., and triethylene glycol dibenzoate freezes from46-48° C. Unexpectedly, all of the present ester compositions areliquids below 28° C. The actual freezing point of any specific estercomposition will be determined by the relative concentrations of theconstituent esters.

The Aromatic Carboxylic Acid

Aromatic carboxylic acids suitable for preparing the present liquidester compositions can be represented by the general formula ArC(O)OH,wherein Ar represents a phenyl or methylphenyl radical. The class ofcarboxylic acids includes benzoic acid and the isomeric toluic acids. Itwill be understood by those skilled in the art that the correspondinganhydrides and acyl halides can be used in places of the carboxylicacids.

The Glycol Mixture

The alcohol portions of the solid esters of the present compositions arederived from diethylene glycol and triethylene glycol.

The relative concentrations of the esters derived from each of the tworequired oligomeric ethylene glycols used to prepare the presentcompositions is critical to obtaining compositions that are liquid below28° C. The ester derived from diethylene glycol constitutes from 55 to90 weight percent, preferably from 55 to 65 weight percent of themixture of esters derived from di- and triethylene glycol.

The present ester compositions can be obtained by first preparing eachof the esters individually using any of the known methods for preparingthis class of compounds. Following purification the esters are meltedprior to or after being combined in the desired proportions.

In accordance with a preferred method, the present ester compositionsare prepared in situ by reacting benzoic acid or one of the isomerictoluic acids with a mixture of diethylene glycol and triethylene glycol.The relative concentration of each glycol is calculated to yield anester composition within the scope of the present invention, assumingthat substantially all of the glycols react with the acid.

Other glycols such as ethylene glycol, propylene glycol and dipropyleneglycol can be included in the mixture of glycols used to prepare thepresent ester compositions, so long as the presence of these additionalglycols does not detract from the objectives of the present invention.

Reaction conditions and apparatus required to prepare esters from thecorresponding carboxylic acid(s) and mono- or polyhydric alcohol(s) aresufficiently well described in the prior art that a detailed descriptionin the present specification is not required. As taught hereinbefore,the corresponding acyl halides or anhydrides can be used in place of theacid. Reactions using these alternative reactants are described in theprior art.

To accelerate formation of the present ester compositions, the reactionmixture containing the benzoic or toluic acid and mixture of glycols ispreferably heated to the boiling point while the water formed as aby-product is continuously removed by distillation from the reactionmixture. Catalysts such as mineral acids and alkyl titanates can bepresent in the reaction mixture, and a low boiling hydrocarbon such ashexane can be present in the reaction mixture to facilitate removal ofthe water.

The esters can be purified by neutralization of and acid catalystsand/or removal of volatile impurities under reduced pressure.

Use of the Present Liquid Ester Compositions as Plasticizers for OrganicPolymers

The liquid ester compositions of the present invention are particularlyuseful as plasticizers to improve the processability and physicalproperties of both rigid and non-rigid organic polymers.

Polymers preferred for use with the present ester composition includepolyvinyl chloride and copolymers derived from vinyl chloride and atleast one additional copolymerizable mono- or diolefinically unsaturatedcompounds, including but not limited to vinylidene chloride, vinylesters of carboxylic acids such as vinyl acetate, and vinyl propionate,esters of ethylenically unsaturated acids such as the alkyl acrylatesand -methacrylates. Preferably at least 70 percent of the repeatingunits of these copolymers are derived from vinyl chloride.

When used as plasticizers, the present ester compositions can be usedalone or in combination with one or more plasticizers known to thoseskilled in the art to achieve a desired combination of processabilityand properties in the final polymer composition.

The concentration of plasticizer(s) in any given polymer composition canvary widely, based on the desired properties and intended use of thecomposition. Concentrations of from 1 to 200 parts of plasticizer perhundred parts by weight of resin (phr) have been reported, however thisrange is preferably from 10 to 100 phr.

The types of polymer compositions into which the present liquid estercompositions can be advantageously incorporated as additives include butare not limited to vinyl flooring laminates, latex caulks, adhesives,coating compositions that are applied as liquids or finely dividedsolids, and inks.

The ester compositions of this invention are also useful asseal-swelling additives for oils and lubricants

The preparation and use of the liquid ester compositions of thisinvention are described in detail in the following examples, whichshould not be interpreted as limiting the scope of the inventiondescribed in the accompanying claims.

EXAMPLE 1

Ester compositions were prepared by combining in glass containers soliddiethylene glycol benzoate (DEGB) and triethylene glycol benzoate (TEGB)in the proportions listed in Table 1. Each of the resultant mixturesweighed ten grams and was heated in an oven maintained at a temperatureof 80° C. for a period of time sufficient to form a liquid. Each of theliquid compositions was then placed for 24 hours in a freezer maintainedat a temperature of −12° C. After 24 hours the containers were examinedfor evidence of crystallizatic The compositions of each sample and theresults of the examination are recorded in Table 1.

TABLE 1 Weight Percent DEGDB TEGDB Physical State at −12° C. 100 0 Solid(c) 0 100 Solid (c) 75 25 Liquid 65 35 Liquid 55 45 Liquid 90 10 Liquidc = Comparative Example

EXAMPLE 2 Polyvinyl Chloride Resilient Flooring

This example demonstrates the use of the present ester compositions asplasticizers for resilient flooring applications. Resilient flooringgenerally consists of at least layers of a vinyl polymer plastisol on adimensionally stable substrate. The plastisol used as the top layer isclear and provides wear resistance. The next layer is a vinyl foamprepared using a plastisol containing a chemical blowing agent.Plasticizers that are used are selected for this application arerequired to be effective, stable, provide stain resistance andprocessability.

A blend of diethylene glycol dibenzoate, triethylene glycol dibenzoateand di-2-ethylhexyl adipate in the weight ratio of 1.0 to 0.55 to 0.27,referred to below as blend A, was tested in resilient flooringlaminates.

Tables 2 to 4 list the formulations evaluated. The formulations wereprepared by mixing the ingredients on a low speed, high intensity mixerand degassing. The foam layer was coated onto a ceramic felt backing andgelled at 130° C. for one minute in a Mathus oven. The top layer wasthen applied and the construct was fused at 190° C. for one and a halfminutes. Tables 4 to 8 list the property data obtained from theconstructs prepared.

TABLE 2 Top Coat Formulation Parts By Ingredient IdentificationManufacturer Weight GEON 173 PVC Dispersion GEON 100 Resin PlasticizerBlend A Present 36 Invention Diluent Isodecyl benzoate Velsicol 12Plasticizer PEG 400 Polyethylene Stepan 1.4 Monolaurate glycol 400molecular weight monolaurate Therm-Chek Mixed metal Ferro 3.0 1776stabilizer Stabilizer Epoxidized soy Velsicol 2.0 bean oil

TABLE 3 Foam Layer Formulation Parts By Ingredient IdentificationManufacture Weight GEON 121 A PVC dispersion GEON 68.8 resin GEON 217PVC blending resin GEON 31.2 Plasticizer Blend A — 24.3 Diluent Isodecylbenzoate Velsicol 19.4 Plasticizer AZO Azodicarbonamide — 12.8Dispersion dispersion (Table 3) PEG 400 Polyethylene Stepan 1.5Monolaurate glycol 400 molecular weight monolaurate Atomite CalciumCarbonate E.C.C. 14.8

TABLE 4 AZO Dispersion Formulation (For Use in Table 3) Parts ByIngredient Identification Manufacturer Weight Plasticizer Blend A — 36.4Diluent Isodecyl benzoate Velsicol 12 Plasticizer PEG 400 PolyethyleneStepan 1.0 Monolaurate Glycol 400 molecular weight monolaurate CELLOGENAZ, Blowing agent Uniroyal 13.2 3990, Chemical azodicarbon- amide AsacoAZO Activator Asaco 3.2 77S, Zinc Oxide TiPure R-900 Pigment Dupont 26TiO₂

TABLE 5 Resilient Flooring Screen Data Top Coat Plastisol Test ParameterBrookfield RVT Low Shear Viscosity, 23° C., ASTM D-1824 Initial and 2hours, Pa · s 2.5 RPM 5.3  20 RPM 3.7 24 Hours, Pa · s 2.5 RPM 6.5  20RPM 4.5 3 Days, Pa · s 2.5 RPM 9.6  20 RPM 6.2 Ratios of 3 Day/InitialViscosity 2.5 RPM 1.8  20 RPM 1.7 High Shear Viscosity, Pa · s, ASTMD-1823, 23° C., @  10 psi 5.2  40 psi 12.6  70 psi 17.6 100 psi 20.7

TABLE 6 Resilient Flooring Screen Data Foam Layer Plastisol TestParameter Brookfield RVT Low Shear Viscosity, 23° C., ASTM D-1824Initial and 2 hours, Pa · s 2.5 RPM 8.8  20 RPM 5.4 24 Hours, Pa · s 2.5RPM 9.8  20 RPM 5.8 3 Days, Pa · s 2.5 RPM 16.3  20 RPM 7.1 Ratio of 3Day/Initial viscosity 2.5 RPM 1.9  20 RPM 1.3 High Shear Viscosity,Pa_s, 23° C., ASTM D-1823  10 psi 4.9  40 psi 10.5  70 psi 13.8 100 psi15.3 Foam Blow Ratio (Final thickness 3.8/1 to initial thickness priorto fusion) Foam Blown quality, visual Fair assessment

TABLE 7 Resilient Flooring Screen Data Construct (Top Over Foam) TestParameter Stain Resistance, Visual and instrumental reading Oil BrownDye, 1% Sln 5 (0 = best and 10 = worst) Initial Rating, ΔE 9.9 Aged @70° C. 1 Week, ΔE 4 (8.5) 2 Weeks, ΔE 5 (7.4) 3 Weeks, ΔE 3 (5.8) 4Weeks, ΔE 2 (3.6) Brown Polish, (B)  6 (55.2) Mustard 0 Black Marker, ΔE6 (25)  Vinyl Heat Stability, 200° C., visual estimate to totaldiscoloration, % Rating after 2.5 min. 5 Rating after 5 min 15 Ratingafter 7.5 min. 30 Rating after 10 min. 60 Rating after 12.5 min. 100

TABLE 8 Resilient Flooring Screen Data Laminate (Top Over Foam) TestParameter Heat Resist., 70° C., Int. ΔE 12.2 Against standard whiteplate) ΔE, 1 week 25.8 ΔE, 2 week 30.9 ΔE, 3 week 33.9 UV LightResistance (Atlas UV chamber) ΔE after, Initial 18.3 (Against standardwhite plate) 100 hours 12.2 200 Hours 12.3 300 Hours 11.5 400 Hours 15.2500 Hours 17.0

The data in the preceding tables demonstrate that blend A is aneffective plasticizer for resilient flooring applications.

EXAMPLE 3

This example demonstrates the utility of the present liquid estercompositions in compositions intended for use as latex caulk. This typeof caulk is used to seal cracks and fill gaps in new and existingresidential and commercial buildings. A caulk consists basically of apolymeric binder and fillers. Compatible plasticizers are used in caulksto increase polymer solids and flexibility, improve adhesion and lowtemperature performance without adversely affecting storage stability orapplication properties of the formulation. A liquid ester composition ofthe present invention containing diethylene glycol dibenzoate,triethylene glycol dibenzoate and dipropylene glycol dibenzoate in theweight ratio of 1:0.5:0.5, referred to hereinafter as blend B, wasincorporated into a latex caulk formulation to determine the utility ofthe present ester compositions for this application.

To function effectively a plasticizer must be compatible with the basepolymer. To determine the compatibility of blend B with a conventioncaulk polymer, a blend of a caulk polymer emulsion and blend B wasprepared using the types and amounts of ingredients listed in Table 9.

A compatible plasticizer should increase the viscosity of the emulsion.Data in Table 10 demonstrate that blend B increased the viscosity of thebase emulsion. To further evaluate the compatibility of blend B with thecaulk polymer, a 0.006 inch-thick film of the caulk formulation wasapplied to a glass plate using a draw down bar and allowed to dry fortwenty four hours. The data in Table 11 demonstrate that the film wasclear and tacky, which is indicative of compatibility between the caulkformulation and the plasticizer.

Blend B was incorporated into a typical latex caulk formulation. Theingredients listed in Table 12 were mixed in a low speed, high intensitymixer. The stability, adhesions, tensile strength and hardness of thecaulk formulation were determined, and the data summarized in Tables 13and 14. These data demonstrate that Blend B, a liquid ester compositionof the present invention, functions well as a plasticizer for latexcaulks.

TABLE 9 Caulk Polymer/Plasticizer Compatibility Data: Formulation Partsby Parts by Weight, Weight, Ingredient Wet Dry Caulk Emulsion 100 100Triton X-405 27.5 50.1 Blend B 1.7 3.1 (plasticizer)

TABLE 10 Compatibility Data of Blend B With Rhoplex(R) 1785Compatibility @ RT Storage Initial 1 Day Appearance Clear Tack High 7Day Appearance Clear Tack High 28 Day Appearance Clear Tack High @ 50°C. Storage 1 Day Appearance Clear Tack High 7 Day Appearance Clear TackHigh 28 Day Appearance Clear Tack High Note: The plasticizer wasincorporated into the base emulsion at a level of 27.5 parts into 100parts of the wet emulsion with 1.65 parts of Triton X-405. Theplasticizer is at a level of 50% on the resin solids.

TABLE 11 Caulk Emulsion Viscosity Response Data: Rhoplex 1785 BrookfieldRVT Viscosities, RT, Pa · s Initial 2.5 RPM 20  20 RPM 7 One Hour 2.5RPM 26  20 RPM 8 Two Hours 2.5 RPM 29  20 RPM 8 24 Hours 2.5 RPM 44  20RPM 12 3 Days 2.5 RPM 34  20 RPM 10 Note: Viscosity of neat emulsion is0.6 Pa · s @ 2.5 RPM and 0.3 Pa · s @ 20 RPM. With the X-405 it is 1 Pa· s @ 2.5 RPM and 3 Pa · s @ 20 RPM's.

TABLE 12 Latex Caulk Formulation Raw Material Manufacturer PoundsGallons RHOPLEX 1785 Rohm & Haas 417.2 46.73 Water 26.9 3.23 TritonX-405 Rohm & Haas 9.2 1 Ethylene Glycol Union Carbide 12.5 1.35 Tamol850 Rohm & Haas 1.2 0.12 Thickener, Hercules 1 0.09 Natrosol(R) 250 MXRDispersant, KTPP Calgon 1 0.05 Blend B Present 114.7 13.82 InventionMineral Spirits, Exxon 20 3.05 Varsol(R) #1 Adhesion Dow Corning 0.570.06 Promoter, Silane Z-6040 Extender, Calcium E.C.C. 735 32.6Carbonate, Drikilite(R) Pigment, Titanium Dupont 10 0.3 Dioxide, TiPureR-901 Ammonium Fisher 3.5 0.39 Hydroxide, 28% Total 1352.77 102.79 Note:Rohm & Haas formulation AS-85-1 used.

TABLE 13 Caulk Package Stability and Viscosity Data Test ParameterInitial Viscosity, Brookfield HAT, Helipath, RT, Pa · s 1 Day 2300 7 Day2700 Gunability, ASTM C-731 1 Day, g/sec, RT 6.7 7 Day, g/sec., RT 5.528 Day, g/sec, RT 2.4 After 28 Days at 50° C. 2.6 After 5 cycles F/T 3.1

TABLE 14 Physical Properties of Caulk Property Low Temp. Flex., 1″mandrel @ −24° C. Pass Shore A, 3 Week @ RT Initial, 1 sec 23 10 sec. 13Tensile, ASTM D-638 Maximum stress, psi 43, (1) Elongation, % 680 180°Peel Adhesion, U.S. 230 Specification test Aluminum Lb/linear inch 6.5,(1.6) Failure mode CP/C Wood, Ponderosa Pine Lb/linear inch 10.1 (2.4)Failure mode A/C Wood Channel Crack None Tack Free Time, min. 9Completion of Cure, days 7

EXAMPLE 4 Latex Adhesive Applications

A latex adhesive is used to adhere a porous substrate to another porousor a non porous substrate. Latex adhesives are used in a large varietyof applications from paper and paperboard packaging to use to glue woodfurniture. A latex adhesive may consist of only a polymeric binder, butin most instances other polymer modifiers are used to formulate anadhesive for a specific purpose. In most instances a plasticizer is usedto formulate an adhesive based on homopolymers such as polyvinylacetate, but are just as often are used to modify copolymer-basedadhesives. An effective, compatible plasticizer is used in a latexadhesive to thicken the base emulsion (viscosity response), to increaseflexibility, to reduce glass transition temperature, improve adhesionsand low temperature performance, extend open time, shorten set time andreduce heat seal temperature. A blend of diethylene glycol dibenzoate,triethylene glycol dibenzoate and dipropylene glycol dibenzoate in theweight ratio of 1 to 0.5 to 0.5 (blend C) was incorporated in latexadhesive formulations based on both homopolymer and copolymer emulsionsto assess the utility of plasticizers containing the present liquidester blends for this application.

To function properly a plasticizer must be compatible with the basepolymer. To determine the compatibility of blend C with adhesivepolymers, adhesives based on a polyvinyl acetate homopolymer and a vinylacetate/ethylene copolymer were prepared. The formulations are listed inTable 15, and the adhesives were prepared by stirring the plasticizerinto the base emulsions. To test the compatibility of the plasticizer, asix mil-thick film of each adhesive was applied to glass plates using adraw down bar and dried for twenty four hours. All the films wereclearer than the base emulsion and free of plasticizer exudation,indicating compatibility at the level of plasticizer tested.

The adhesive performance data are also listed in Table 15.

The emulsion viscosity response, open time, set time and caulkperformance data indicate that mixture c of the present inventionfunctions well as an adhesive plasticizer.

TABLE 15 Adhesive Formulations and Performance Data Formulation 1 2 3 4Ingredient Vinac(R) XX-230 100 89.5 (Homopolymer) Airflex(R) 300 10089.5 (Copolymer) Blend C 10.5 10.5 Data Plasticizer compatibilityVinac(R) XX-230 Dry Very Very Very Very film appearance, after HazySlight Hazy Slight 24 hours Haze Haze Plasticizer viscosity responseViscosity after 1 hour of preparation (ASTM D-1824) 2.5 RPM's, Pa · s 45.8 4 19  20 RPM's, Pa · s 2.6 3.8 2 10 Viscosity after 24 Hours 2.5RPM's, Pa · s 4 5 4 20  20 RPM's, Pa · s 2.6 3.3 2 11 Set time, seconds15 10 13 8 Open time, seconds <10 33 8 23 Adhesions, Visual rating with0 = none and 10 = Complete bonding, to paper coated with: X-300 0 0 — —Nomar(R) 70 5 9 — —

EXAMPLE 5

Blends of diethylene glycol dibenzoate, triethylene glycol dibenzoate,and a third plasticizer were prepared and tested in the followingmanner. A glass vial was filled with 10 grams of test material andplaced in a freezer at −12° C. for 24 hours. After 24 hours, the vialswere examined for signs of crystallization. The results are in Table 16.Samples were rated as a ‘Pass’ if there were no signs ofcrystallization.

TABLE 16 Weight percent in Blend DOA¹ DOP² DPGDB³ DEGDB⁴ TEGDB⁵ Rating 00 50 25 25 pass 0 50 0 25 25 pass 50 0 0 25 25 pass ¹DOA isdi-2-ethylhexyl phthalate ²DOP is di-2-ethylhexyl phthalate. ³DPGDB isdipropylene glycol dibenzoate. ⁴DEGDB is diethylene glycol dibenzoate.⁵TEGDB is triethylene glycol dibenzoate.

The third plasticizer acts as a freeze point depressant for the twosolid esters and extends the useful range of the present compositions.

That which is claimed is:
 1. An organic polymer composition comprisingat least one thermoplastic organic polymer and an amount sufficient toplasticize said polymer of a liquid ester composition comprising 1) afirst diester of the formula ArC(O) (OCH₂CH₂)₂O(O) CAr and 2) a seconddiester of the formula ArC(O) (OCH₂CH₂)₃O(0) CAr; wherein Ar representsa phenyl or methylphenyl radical, and the freezing point of saidcomposition is below the freezing points of said first and seconddiesters.
 2. The composition of claim 1 wherein the weight ratio of saidfirst diester to said second diester is from 1.22:1 to 9:1 and Arrepresents a phenyl radical.
 3. An organic polymer compositioncomprising at least one thermoplastic organic polymer and an amountsufficient to plasticize said polymer of a liquid ester compositioncomprising 1) a first diester of the formula ArC(O) (OCH₂CH₂)₂O(O) CAr;2) a second diester of the formula ArC(O) (OCH₂CH₂)₃O(O) CAr; and 3) atleast one additional ester that is a liquid at 25° C.; wherein Arrepresents a phenyl or methylphenyl radical, the freezing point of saidcomposition is below the freezing points of said first and seconddiesters and wherein the combined weights of said first and seconddiesters constitute at least 50 weight percent of said composition. 4.The composition of claim 3 where the weight ratio of said first diesterto said second diester is from 0.5:1 to 9:1.
 5. The composition of claim3 wherein said additional ester is at least one member selected from thegroup consisting of 1) diesters derived from benzoic acid and diolscontaining from 3 to 10 carbon atoms, 2) esters derived from benzoicacid and monohydric alcohols containing from 4 to 12 carbon atoms, 3)aliphatic esters of the formula R¹O(O)C(CH₂)_(m)C(O)OR¹, wherein each R¹is an alkyl radical individually selected from the group consisting ofalkyl radicals containing from 8 to 12 carbon atoms, and m represents aninteger from 2 to 8, and 4) esters derived from phthalic acid andalcohols containing from 4 to 12 carbon atoms, wherein the combinedweight of additional esters constitutes from 10 to 35 weight percent ofsaid composition and said additional ester is a liquid at 28° C.
 6. Thecomposition of claim 5 wherein said additional esters are selected fromthe group consisting of di(2-ethylhexyl) adipate and di(2-ethylhexyl)phthalate, and dipropylene glycol dibenzoate.
 7. The composition ofclaim 1 wherein the organic polymer is selected from the groupconsisting of polyvinyl chloride and copolymers derived from vinylchloride and at least one additional copolymerizable olefinicallyunsaturated compound selected from the group consisting of vinylidenechloride, vinyl esters of carboxylic acids, and esters of ethylenicallyunsaturated carboxylic acids.
 8. The composition of claim 3 wherein theorganic polymer is selected from the group consisting of polyvinylchloride and copolymers derived from vinyl chloride and at least oneadditional copolymerizable olefinically unsaturated compound selectedfrom the group consisting of vinylidene chloride, vinyl esters ofcarboxylic acids, and esters of ethylenically unsaturated carboxylicacids.
 9. The composition of claim 7 wherein at least 70 percent of therepeating units of said copolymers are derived from vinyl chloride. 10.The composition of claim 8 wherein at least 70 percent of the repeatingunits of said copolymers are derived from vinyl chloride.
 11. Anadhesive composition comprising the polymer composition of claim
 1. 12.An adhesive composition comprising the polymer composition of claim 3.13. A latex caulk composition comprising the polymer composition ofclaim
 1. 14. A latex caulk composition comprising the polymercomposition of claim
 3. 15. A liquid or solid coating compositioncomprising the polymer composition of claim
 1. 16. A liquid or solidcoating composition comprising the polymer composition of claim 3.